Phosphorous Containing Compounds and Uses Thereof

ABSTRACT

The invention relates to phosphorous-containing compounds useful as antiwear additive components, lubricant additive compositions and lubricant compositions each comprising such compounds, methods for making and using the same, including methods of lubricating machines and machine parts and methods of extending the useful life of elastomeric seal components of such machines.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/415,492, filed Oct. 31, 2016, the entire contents ofwhich are hereby incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to phosphorous-containing compounds useful asantiwear additive components, lubricant additive compositions andlubricant compositions each comprising such compounds, and methods formaking and using the same.

BACKGROUND OF THE INVENTION

Traditionally, anti-wear components of lubricating compositions compriseacidic organophosphates salted with amines and/or metal ions. Thesecomponents provide good anti-wear protection but other performanceattributes can suffer including poor seal durability, reduced oxidativestability, and inadequate corrosion inhibition. Phosphorus- andsulfur-containing compounds are understood to be essential inlubricating fluids to protect surfaces from wear as a result of theextreme pressures encountered by the surfaces. As a result, these fluidshave traditionally been harmful to seals (dynamic and static) and yellowmetals. In addition, there is increasing pressure from regulatoryagencies to remove amines and metal ions from lubricating fluids todecrease the environmental impact of such components. Due to theseincreasing environmental concerns, the presence of amines and metal ionsin antiwear additives is becoming less desirable. Accordingly, there isa need to develop novel antiwear compounds contain little or no aminesor metal ions.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the invention relates to a compound of formula (I)

-   -   or a tribologically acceptable salt thereof,    -   wherein A is:

-   -   each R¹ is the same or different and is independently selected        from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   each R² and R³ are independently selected from H, alkyl,        alkenyl, cycloalkyl and cycloalkylalkyl;    -   Y is selected from the group consisting of alkyl, alkoxyalkyl,        benzyl, and —R⁴-R⁵-R⁶;    -   R⁴ is alkylene;    -   R⁵ is selected from the group consisting of a bond, alkylene;        —C(O)— and —C(R⁷)—;    -   R⁶ is selected from the group consisting of alkyl, hydroxyalkyl,        hydroxyalkyleneoxy, hydroxy and alkoxy;    -   R⁷ is hydroxy;    -   m is an integer from 2 to 8;    -   X₁ is R⁸ or Z;    -   X₂ is selected from the group consisting of R⁸,

-   -   R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl; and    -   Z is

-   -   wherein when X₂ is R⁸, X₁ is Z;    -   W₁-W₁₂ are each independently O or S, and at least one of W₁-W₁₂        is O.

In a second aspect, the invention provides a lubricant additivecomposition comprising the compound of formula (I).

In a third aspect, the invention provides a lubricant compositioncomprising a major amount of an oil of lubricating viscosity or a greaseprepared therefrom and a minor amount of the compound of formula (I).

In as fourth aspect, the invention provides a lubricant compositioncomprising a major amount of an oil of lubricating viscosity or a greaseprepared therefrom and a minor amount of a lubricant additivecomposition of the present invention.

In a fifth aspect, the invention provides a method of lubricating movingmetal surfaces comprising lubricating the metal surfaces with alubricant composition of the present invention.

In a sixth aspect, the invention provides a method of extending thefunctional life of an elastomeric seal that contacts a lubricating orfunctional fluid composition, the method comprising contacting the sealwith an effective amount of a lubricating composition of the presentinvention

DETAILED DESCRIPTION OF THE INVENTION

The invention disclosed herein relates to novel phosphate andthiophosphate compounds that are useful as antiwear agents and methodsfor preparing the same. The invention also provides lubricant additivecompositions and lubricant compositions comprising the compounds, andmethods of using the same.

The compounds of the present invention include compounds of formula (I)

-   -   or a tribologically acceptable salt thereof,    -   wherein A is:

-   -   each R¹ is the same or different and is independently selected        from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   each R² and R³ are independently selected from H, alkyl,        alkenyl, cycloalkyl and cycloalkylalkyl;    -   Y is selected from the group consisting of alkyl, alkoxyalkyl,        benzyl, and —R⁴-R⁵-R⁶;    -   R⁴ is alkylene;    -   R⁵ is selected from the group consisting of a bond, alkylene;        —C(O)— and —C(R⁷)—;    -   R⁶ is selected from the group consisting of alkyl, hydroxyalkyl,        hydroxyalkyleneoxy, hydroxy and alkoxy;    -   R⁷ is hydroxy;    -   m is an integer from 2 to 8;    -   X₁ is R⁸ or Z;    -   X₂ is selected from the group consisting of R⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl;and

-   -   Z is

-   -   wherein when X₂ is R⁸, X₁ is Z;    -   W₁-W₁₂ are each independently O or S, and at least one of W₁-W₁₂        is O.

In one embodiment, each R¹ is the same or different and is independentlyselected from C₁-C₃₀alkyl, C₂-C₃₀alkenyl, cycloalkyl, cycloalkylalkyl,aryl and aralkyl, wherein said aryl and aralkyl are optionallysubstituted with one to three substituents each independently selectedfrom C₁-C₁₀alkyl and C₂-C₁₀alkenyl.

In another embodiment, each of W₁-W₁₂ is O. In certain embodiments, W₁,W₂, W₅ and W₆ are each O. In a further embodiment, W₃ and W₄ are both S.In another embodiment, W₃ and W₄ are both O. In one embodiment, at leasthalf of the group of W₁-W₁₂ are O and the remaining are S.

In another embodiment, each R¹ is the same or different and isindependently C₃-C₁₀alkyl.

In some embodiments, m is an integer from 2 to 5. In certainembodiments, m is 2.

In one embodiment, each R² and R³ are independently selected from H andC₁-C₁₀alkyl. In another embodiment, for each instance of A, one R² isalkyl and the remaining instances of R² and R³ are H. In a furtherembodiment, when R² is alkyl, the alkyl is C₁-C₁₀alkyl.

In a further embodiment, X₂ is

In another embodiment, X₂ is R⁸.

In another embodiment, Y is —R⁴-R⁵-R⁶. In a further embodiment, Y is—R⁴-R⁵-R⁶ and R⁴ is alkylene, R⁵ is —C(O)—, and R⁶ is hydroxy or alkoxy.

In one embodiment, R⁸ is C₁-C₁₀ alkyl.

In one embodiment, each R¹ is independently selected from C₁-C₃₀ alkyl.In another embodiment, each R¹ is independently selected from C₃-C₁₀alkyl. In another embodiment, each R¹ is independently selected fromC₃-C₆ alkyl. In certain embodiments, each R′ is the same as every otherR¹.

In one embodiment, Y is C₁-C₂₀ alkyl.

In one embodiment, the invention provides a compound of formula (Ia)

-   -   or a tribologically acceptable salt thereof,    -   each R¹ is the same or different and is independently selected        from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   each R² is independently selected from alkyl, alkenyl,        cycloalkyl and cycloalkylalkyl;    -   Y is selected from the group consisting of alkyl, alkoxyalkyl,        benzyl, and —R⁴-R⁵-R⁶;    -   R⁴ is alkylene;    -   R⁵ is selected from the group consisting of a bond, alkylene;        —C(O)— and —C(R⁷)—;    -   R⁶ is selected from the group consisting of alkyl, hydroxyalkyl,        hydroxyalkyleneoxy, hydroxy and alkoxy;    -   R⁷ is hydroxy;    -   X₂ is selected from the group consisting of R⁸,

-   -   R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   Z is

and

-   -   W₁-W₁₄ are each independently O or S, and at least one of W₁-W₁₄        is O.

In one embodiment, each R¹ is the same or different and is independentlyselected from C₁-C₃₀alkyl, C₂-C₃₀alkenyl, cycloalkyl, cycloalkylalkyl,aryl and aralkyl, wherein said aryl and aralkyl are optionallysubstituted with one to three substituents each independently selectedfrom C₁-C₁₀alkyl and C₂-C₁₀alkenyl.

In another embodiment, each of W₁-W₁₄ is O.

In another embodiment, each R¹ is the same or different and isindependently C₁-C₁₀alkyl.

In one embodiment, each R² and R³ are independently selected from H andC₁-C₁₀alkyl. In another embodiment, for each instance of A, one R² isalkyl and the remaining instances of R² and R³ are H. In a furtherembodiment, when R² is alkyl, the alkyl is C₁-C₁₀alkyl.

In a further embodiment, X₂ is

In another embodiment, X₂ is R⁸.

In another embodiment, Y is —R⁴-R⁵-R⁶. In a further embodiment, Y is—R⁴-R⁵-R⁶ and R⁴ is alkylene, R⁵ is —C(O)—, and R⁶ is hydroxy or alkoxy.

In one embodiment, R⁸ is C₁-C₁₀ alkyl.

In one embodiment, each R¹ is independently selected from C₁-C₃₀ alkyl.In another embodiment, each R¹ is independently selected from C₃-C₁₀alkyl. In another embodiment, each R¹ is independently selected fromC₃-C₆ alkyl. In certain embodiments, each R¹ is the same as every otherR¹.

In one embodiment, Y is C₁-C₂₀ alkyl.

In one embodiment, the compounds of formula (I) are compounds of formula(II)

-   -   or a tribologically acceptable salt thereof,    -   wherein A is:

-   -   each R¹ is the same or different and is independently selected        from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   each R² and R³ are independently selected from H, alkyl,        alkenyl, cycloalkyl and cycloalkylalkyl;    -   Y is selected from the group consisting of alkyl, alkoxyalkyl,        benzyl, and —R⁴-R⁵-R⁶;    -   R⁴ is alkylene;    -   R⁵ is selected from the group consisting of a bond, alkylene;        —C(O)— and —C(R⁷)—;    -   R⁶ is selected from the group consisting of alkyl, hydroxyalkyl,        hydroxyalkyleneoxy, hydroxy and alkoxy;    -   R⁷ is hydroxy;    -   m is an integer from 2 to 8;    -   X₁ is R⁸ or Z;    -   X₂ is selected from the group consisting of R⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl;and

-   -   Z is

-   -   wherein when X₂ is R⁸, X₁ is Z;    -   W₁, W₃, W₅, W₇, W₉, and W₁₁ are each independently O or S, and        at least one of W₁, W₃, W₅, W₇, W₉, and W₁₁ is O.

In one embodiment, each R¹ is the same or different and is independentlyselected from C₁-C₃₀alkyl, C₂-C₃₀alkenyl, cycloalkyl, cycloalkylalkyl,aryl and aralkyl, wherein said aryl and aralkyl are optionallysubstituted with one to three substituents each independently selectedfrom C₁-C₁₀alkyl and C₂-C₁₀alkenyl.

In another embodiment, W₁, W₃, W₅, W₇, W₉, and W₁₁ are each O.

In another embodiment, each R¹ is the same or different and isindependently C₃-C₁₀alkyl.

In some embodiments, m is an integer from 2 to 5. In certainembodiments, m is 2.

In one embodiment, each R² and R³ are independently selected from H andC₁-C₁₀alkyl. In another embodiment, for each instance of A, one R² isalkyl and the remaining instances of R² and R³ are H. In a furtherembodiment, when R² is alkyl, the alkyl is C₁-C₁₀alkyl.

In a further embodiment, X₂ is

In another embodiment, X₂ is R⁸.

In another embodiment, Y is —R⁴-R⁵-R⁶. In a further embodiment, Y is—R⁴-R⁵-R⁶ and R⁴ is alkylene, R⁵ is —C(O)—, and R⁶ is hydroxy or alkoxy.

In one embodiment, R⁸ is C₁-C₁₀ alkyl.

In one embodiment, each R¹ is independently selected from C₁-C₃₀ alkyl.In another embodiment, each R¹ is independently selected from C₃-C₁₀alkyl. In another embodiment, each R¹ is independently selected fromC₃-C₆ alkyl. In certain embodiments, each R¹ is the same as every otherR¹.

In one embodiment, Y is C₁-C₂₀ alkyl.

In one embodiment, the invention provides a compound of formula (IIa)

-   -   or a tribologically acceptable salt thereof,    -   each R¹ is the same or different and is independently selected        from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl;    -   each R² is independently selected from alkyl, alkenyl,        cycloalkyl and cycloalkylalkyl;    -   Y is selected from the group consisting of alkyl, alkoxyalkyl,        benzyl, and —R⁴-R⁵-R⁶;    -   R⁴ is alkylene;    -   R⁵ is selected from the group consisting of a bond, alkylene;        —C(O)— and —C(R⁷)—;    -   R⁶ is selected from the group consisting of alkyl, hydroxyalkyl,        hydroxyalkyleneoxy, hydroxy and alkoxy;    -   R⁷ is hydroxy;    -   X₂ is selected from the group consisting of R⁸,

-   -   R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and        aralkyl, wherein said aryl and aralkyl are optionally        substituted with one to three substituents each independently        selected from alkyl and alkenyl; and    -   Z is

-   -   W₁, W₃, W₅, W₇, W₉, W₁₁ and W₁₄ are each independently O or S,        and at least one of W₁, W₃, W₅, W₇, W₉, W₁₁ and W₁₄ is O.

In one embodiment, the compound of formula I is selected from

As used herein, the term “alkyl,” as well as the alkyl moieties of othergroups referred to herein (e.g., alkoxyl) may be linear or branchedchain saturated hydrocarbons. Alkyl may preferably contain from 1 to 30carbon atoms, such as 1 to 20 carbon atoms, or 1 to 10 carbon atoms,unless otherwise specified. Representative examples of alkyl groupsinclude, but are not limited to, methyl, ethyl, propyl, butyl, pentyl,neopentyl, 2-ethylhexyl, and the like.

As used herein, the term “alkenyl” means a straight or branchedhydrocarbon chain containing at least one carbon-carbon double bond.Unless indicated otherwise, alkenyl may preferably contain from 2 to 30carbon atoms, such as 2 to 20 carbon atoms, or 2 to 10 carbon atoms. Forexample, the term “C₂-C₄alkenyl” means an alkenyl group containing 2-4carbon atoms. Representative examples of alkenyl include, but are notlimited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl,4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl, and 3-decenyl.

As used herein, the term “substituted” refers to wherein one or morehydrogen atoms are each independently replaced with a non-hydrogensubstituent.

As used herein, the term “alkoxy” refers to an alkyl group attached tothe parent molecular moiety through an oxygen atom.

As used herein, the term “alkenyloxy” refers to an alkenyl groupattached to the parent molecular moiety through an oxygen atom.

As used herein, the term “alkoxyalkyl” refers to a group-alkylene-O-alkyl.

As used herein, the term “alkylene” refers to a methylene orpolymethylene group, i.e., —(CH₂)_(z)—, wherein z is a positive integerfrom 1 to 30.

As used herein, the term “cycloalkyl” means a non-aromatic, monocyclicor polycyclic ring comprising carbon and hydrogen atoms. A cycloalkylgroup can have one or more carbon-carbon double bonds in the ring solong as the ring is not rendered aromatic by their presence.

As used herein, the term “cycloalkylalkyl” means a cycloalkyl group thatis attached to the parent molecular moiety with an alkylene linker groupconsisting of at least one carbon.

As used herein the term “hydroxyalkyl” refers to the group R^(a)-R^(b)—wherein R^(a) is HO— and R^(b) is alkylene.

As used herein the term “hydroxyalkyleneoxy” refers to the groupR^(a)-R^(b)-R^(c) wherein R^(a) is HO—, R^(b) is alkylene and R^(c) is—O—.

As used herein, the symbol “

” when drawn perpendicularly across a bond indicates a point ofattachment of the group. It is noted that the point of attachment istypically only identified in this manner for larger groups in order toassist the reader in rapidly and unambiguously identifying a point ofattachment.

As used herein, the phrase “reactive group” refers to an electrophilicchemical group that is capable of attaching a carbon atom of asubstituent to a sulfur atom in a nucleophilic P—SH group, for example,in a dithiophosphate, or attaching a carbon atom of a substituent to anoxygen atom of a nucleophilic P—OH, for example, in a phosphate. Suchreactive groups are readily recognized by those skilled in the art.Examples of suitable reactive groups in accordance with the presentinvention include alkyl halides, activated alkyl alcohols includingtosylates, triflates and mesylates, epoxides, and acrylate derivatives.In certain embodiments, the reactive group can be selected from1-bromohexadecane, methyl iodide, benzyl bromide, vinyl butyl ether,ethyl acrylate, 1,2-epoxydodecane, acrylic acid, 1,2-epoxydecane, and2-hydroxyethyl acrylate.

As used herein, the phrase “effective amount” means an amount sufficientto provide the desired effect. For example, the compounds of the presentinvention are useful as antiwear agents when incorporated into lubricantcompositions. Therefore, an effective amount of a compound of thepresent invention when incorporated into a lubricant composition can bean amount that improves the antiwear properties of the lubricantcompositions comprising a compound of the instant invention as comparedto the same lubricant composition that does not comprise a compound ofthe instant invention.

As used herein, the terms “oil composition,” “lubrication composition,”“lubricating composition,” “lubricating oil composition,” “lubricatingoil,” “lubricant composition,” “fully formulated lubricant composition,”and “lubricant” are considered synonymous, fully interchangeableterminology referring to the finished lubrication product comprising amajor amount of a base oil plus a minor amount of an additivecomposition. As used herein, the reference to a “major amount” of baseoil and a “minor amount” of additive composition means that thelubricating composition contains an amount of base oil that is more thanthe amount of additive composition on a weight % basis of the totallubricating composition. In certain embodiments, the major amount ofbase oil is 50-99.999 wt % of the total lubricating composition.

Although many of the compounds of formula I are substantially neutral,the present invention also contemplates base addition salts of compoundsof formula I. The chemical bases that may be used as reagents to preparetribologically acceptable base salts of those compounds of formula Ithat are acidic in nature are those that form base salts with suchcompounds. Such base salts include, but are not limited to cations suchas alkali metal cations (e.g., potassium and sodium) and alkaline earthmetal cations (e.g., calcium and magnesium), ammonium or amine additionsalts such as N-methylglucamine-(meglumine), and alkanolammonium andother base salts of tribologically acceptable organic amines, includingbut not limited to alkylamines such as octylamine and oleylamine. Incertain embodiments, the salts of the compounds of formula I are notamine salts.

The phrase “tribologically acceptable salt(s)”, as used herein, unlessotherwise indicated, includes salts of acidic or basic groups which maybe present in the compounds of the present disclosure. As recognizedreadily by the skilled artisan, tribology is a term defining a studythat deals with the design, friction, wear and lubrication ofinteracting surfaces in a relative motion (as in bearings or gears).Tribologically acceptable salts are salts that do not negate orinterfere with the tribological activity of the compounds. The compoundsof the present disclosure that are basic in nature are capable offorming a wide variety of salts with various inorganic and organicacids. The acids that may be used to prepare tribologically acceptableacid addition salts of such basic compounds are those that form acidaddition salts, i.e., salts containing tribologically acceptable anions,such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate,bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate,salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate,ascorbate, succinate, maleate, gentisinate, fumarate, gluconate,glucuronate, saccharate, formate, benzoate, glutamate, methanesulfonate,ethanesulfonate, benzenesulfonate, p-toluenesulfonate and pamoate [i.e.,1,1′-methylene-bis-(2-hydroxy-3-naphthoate)] salts. Compounds of thepresent disclosure that include a basic moiety, such as an amino group,may form tribologically acceptable salts with various amines, inaddition to the acids mentioned above.

The compounds of the present disclosure include all stereoisomers (e.g.,cis and trans isomers) and all optical isomers of compounds of Formula I(e.g., R and S enantiomers), certain positional isomers, as well asracemic, diastereomeric and other mixtures of such isomers. Thoseskilled in the relevant art can readily envision such isomers and theisomers are included within the scope of the present invention.

The compounds and salts of the present disclosure can exist in severaltautomeric forms, including the enol and imine form, and the keto andenamine form and geometric isomers and mixtures thereof. All suchtautomeric forms are included within the scope of the presentdisclosure. Even though one tautomer may be described, the presentdisclosure includes all tautomers of the present compounds.

The compounds of the present invention are contemplated to be used as anadditive in lubricating base oil. As used herein, the term “base oil”refers to oils categorized by the American Petroleum Institute (API)category groups Group I-V oils as well as animal oils, vegetable oils(e.g. castor oil and lard oil), petroleum oils, mineral oils, syntheticoils, and oils derived from coal or shale. The American PetroleumInstitute has categorized these different basestock types as follows:Group I, greater than 0.03 wt percent sulfur, and/or less than 90 volpercent saturates, viscosity index between 80 and 120; Group II, lessthan or equal to 0.03 wt percent sulfur, and greater than or equal to 90vol percent saturates, viscosity index between 80 and 120; Group III,less than or equal to 0.03 wt percent sulfur, and greater than or equalto 90 vol percent saturates, viscosity index greater than 120; Group IV,all polyalphaolefins. Hydrotreated basestocks and catalytically dewaxedbasestocks, because of their low sulfur and aromatics content, generallyfall into the Group II and Group III categories. Polyalphaolefins (GroupIV basestocks) are synthetic base oils prepared from various alphaolefins and are substantially free of sulfur and aromatics.

Groups I, II, and III are mineral oil process stocks. Group IV base oilscontain true synthetic molecular species, which are produced bypolymerization of olefinically unsaturated hydrocarbons. Many Group Vbase oils are also true synthetic products and may include diesters,polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphateesters, polyvinyl ethers, and/or polyphenyl ethers, and the like, butmay also be naturally occurring oils, such as vegetable oils. It shouldbe noted that although Group III base oils are derived from mineral oil,the rigorous processing that these fluids undergo causes their physicalproperties to be very similar to some true synthetics, such as PAOs.Therefore, oils derived from Group III base oils may sometimes bereferred to as synthetic fluids in the industry.

The compounds of the present invention can be added to base oils in theform of a mineral oil or synthetic oil, animal oil, vegetable oil, ormixtures thereof. In general, the mineral oils, both paraffinic andnaphthenic and mixtures thereof can be employed as lubricating oil or asthe grease vehicle. Also contemplated are greases in which any of theforegoing oils are employed as a base.

The compound of the present invention, in addition to other additivecomponents, can be added to a lubricating oil to form a finished fluidhaving a viscosity of at least an SAE 90 or 75W-85. Viscosity indexesfrom about 95 to 130 being preferred. The average molecular weights ofthese oils can range from about 250 to about 800.

Where the lubricant is employed as a grease, the lubricant is generallyused in an amount sufficient to balance the total grease composition,after accounting for the desired quantity of the thickening agent, andother additive components included in the grease formulation. A widevariety of materials can be employed as thickening or gelling agents.These can include any of the conventional metal salts or soaps, such ascalcium, or lithium stearates or hydroxystearates, which are dispersedin the lubricating vehicle in grease-forming quantities in an amountsufficient to impart to the resulting grease composition the desiredconsistency. Other thickening agents that can be employed in the greaseformulation comprise the non-soap thickeners, such as surface-modifiedclays and silicas, aryl ureas, calcium complexes and similar materials.In general, grease thickeners can be employed which do not melt ordissolve when used at the required temperature within a particularenvironment; however, in all other respects, any material which isnormally employed for thickening or gelling hydrocarbon fluids forforming greases can be used in the present invention.

Where synthetic oils, or synthetic oils employed as the vehicle for thegrease, are desired in preference to mineral oils, or in mixtures ofmineral and synthetic oils, various synthetic oils may be used. Typicalsynthetic oils include polyisobutylenes, polybutenes, polydecenes,siloxanes and silicones (polysiloxanes).

The present invention provides lubricant compositions comprising a majoramount of oil of lubricating viscosity or a grease prepared therefromand a minor amount of a compound of the present invention. The compoundof the present invention can be in the lubricant composition in anamount between about 0.001% to 10%, between 0.01% to 5%, between 0.01%to 1.0%, between 0.5% to 2.0%, and between 0.015% to about 0.5% byweight of the total composition. In some embodiments, lubricatingcompositions can contain between about from 0.01% to 0.5%, between about0.01 and about 0.4 wt %, or between about 0.01 and about 0.3 wt %, orbetween about 0.01 and about 0.2 wt %.

As mentioned above, the compounds of the present invention can bereadily formulated into lubricant compositions suitable for use with avariety of machine parts and components. The lubricant compositionscomprising a compound of the present invention can optionally furthercomprise one or more other additive components such that the lubricantcompositions. The list of additive components disclosed below is notexhaustive and additive components not expressly disclosed herein arewell known to the skilled artisan and may also be included in thelubricant compositions. Without limitation, additive components that canbe used in the lubricant compositions of the present invention includeantioxidants, additional antiwear agents, corrosion inhibitors,detergents, extreme pressure agents, viscosity index improvers, andfriction reducers.

In one embodiment, the lubricant composition of the present inventioncomprises a compound of the present invention and at least oneadditional additive composition selected from the group consisting of anantioxidant, antiwear agents, corrosion inhibitor, detergent, extremepressure agent, dispersant, viscosity index improvers, and frictionmodifiers.

The compounds of the present invention can be incorporated into an oilof lubricating viscosity directly. Alternatively, compounds of thepresent invention can be prepared in combination with other lubricantadditives to form a lubricant additive composition. Generally, thelubricant additive composition will further be incorporated into the oilof lubricating viscosity at a particular wt % of the lubricant additivepackage relative to the total weight of the final lubricant composition.The wt % selected is generally referred to as the treat rate and thelubricant composition containing the lubricant additive composition isgenerally referred to as a finished fluid.

In one embodiment the present invention provides a lubricant additivecomposition comprising a compound of the present invention and at leastone additional additive component. The one or more additional additivecomponent(s) can be selected from an antioxidant, antiwear agents,corrosion inhibitor, detergent, extreme pressure agent, viscosity indeximprovers, and friction modifiers.

Antioxidants

Antioxidant compounds are known and include, for example, phenates,phenate sulfides, sulfurized olefins, phosphosulfurized terpenes,sulfurized esters, aromatic amines, alkylated diphenylamines (e.g.,nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine,di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylatedphenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols,hindered phenols, oil-soluble molybdenum compounds, macromolecularantioxidants, or mixtures thereof. A single antioxidant or a combinationof two or more can be used.

The hindered phenol antioxidant may contain a secondary butyl and/or atertiary butyl group as a sterically hindering group. The phenol groupmay be further substituted with a hydrocarbyl group and/or a bridginggroup linking to a second aromatic group. Examples of suitable hinderedphenol antioxidants include 2,6-di-tert-butylphenol,4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol,4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or4-dodecyl-2,6-di-tert-butylphenol. In an embodiment the hindered phenolantioxidant may be an ester and may include, e.g., an addition productderived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein thealkyl group may contain about 1 to about 18, or about 2 to about 12, orabout 2 to about 8, or about 2 to about 6, or about 4 carbon atoms.

Useful antioxidants may include diarylamines and high molecular weightphenols. In an embodiment, the lubricating oil composition may contain amixture of a diarylamine and a high molecular weight phenol, such thateach antioxidant may be present in an amount sufficient to provide up toabout 5%, by weight of the antioxidant, based upon the final weight ofthe lubricating oil composition. In some embodiments, the antioxidantmay be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 toabout 2.5% high molecular weight phenol, by weight, based upon the finalweight of the lubricating oil composition.

Examples of suitable olefins that may be sulfurized to form a sulfurizedolefin include propylene, butylene, isobutylene, polyisobutylene,pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene,tridecene, tetradecene, pentadecene, hexadecene, heptadecene,octadecene, nonadecene, eicosene or mixtures thereof. In an embodiment,hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixturesthereof and their dimers, trimers and tetramers are especially usefulolefins. Alternatively, the olefin may be a Diels-Alder adduct of adiene such as 1,3-butadiene and an unsaturated ester, such as,butylacrylate.

Another class of sulfurized olefin includes sulfurized fatty acids andtheir esters. The fatty acids are often obtained from vegetable oil oranimal oil and typically contain about 4 to about 22 carbon atoms.Examples of suitable fatty acids and their esters include triglycerides,oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often,the fatty acids are obtained from lard oil, tall oil, peanut oil,soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.Fatty acids and/or ester may be mixed with olefins, such as α-olefins.

The one or more antioxidant(s) may be present in ranges of from about 0wt. % to about 20 wt. %, or about 0.1 wt. % to about 10 wt. %, or about1 wt. % to about 5 wt. %, of the lubricating composition.

Antiwear Agents

The compounds of the present invention can be used as antiwear agents.However, in certain embodiments, the lubricant additive compositions andthe lubricant compositions can contain additional antiwear agent(s).Examples of additional suitable antiwear agents include, but are notlimited to, a metal thiophosphate; a metal dialkyldithiophosphate; aphosphoric acid ester or salt thereof; a phosphate ester(s); aphosphite; a phosphorus-containing carboxylic ester, ether, or amide; asulfurized olefin; thiocarbamate-containing compounds including,thiocarbamate esters, alkylene-coupled thiocarbamates, andbis(S-alkyldithiocarbamyl)disulfides; and mixtures thereof. Thephosphorus containing antiwear agents are more fully described inEuropean Patent No. 1490460. The metal in the dialkyl dithio phosphatesalts may be an alkali metal, alkaline earth metal, aluminum, lead, tin,molybdenum, manganese, nickel, copper, titanium, or zinc. A usefulantiwear agent may be a thiophosphate such as zincdialkyldithiophosphate.

The additional antiwear agent may be present in ranges of from about 0wt. % to about 15 wt. %, or about 0.01 wt. % to about 10 wt. %, or about0.05 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. % of thetotal weight of the lubricating composition. In certain embodiments, theadditional antiwear agent(s) are in the form of amine salts and presentin less than or equal to about 1.0 wt %, less than or equal to about 0.5wt % or less than or equal to about 0.25 wt %. In other embodiments, theadditional antiwear agents are not amine salts.

Detergents

The lubricant composition may optionally comprise one or more neutral,low based, or overbased detergents, and mixtures thereof. Suitabledetergent substrates include phenates, sulfur containing phenates,sulfonates, calixarates, salixarates, salicylates, carboxylic acids,phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols,sulfur coupled alkyl phenol compounds and methylene bridged phenols.Suitable detergents and their methods of preparation are described ingreater detail in numerous patent publications, including U.S. Pat. No.7,732,390, and references cited therein.

The detergent substrate may be salted with an alkali or alkaline earthmetal such as, but not limited to, calcium, magnesium, potassium,sodium, lithium, barium, or mixtures thereof. In some embodiments, thedetergent is free of barium. A suitable detergent may include alkali oralkaline earth metal salts of petroleum sulfonic acids and long chainmono- or di-alkylarylsulfonic acids with the aryl group being one ofbenzyl, tolyl, and xylyl.

Overbased detergent additives are well known in the art and may bealkali or alkaline earth metal overbased detergent additives. Suchdetergent additives may be prepared by reacting a metal oxide or metalhydroxide with a substrate and carbon dioxide gas. The substrate istypically an acid, for example, an acid such as an aliphatic substitutedsulfonic acid, an aliphatic substituted carboxylic acid, or an aliphaticsubstituted phenol.

The terminology “overbased” relates to metal salts, such as metal saltsof sulfonates, carboxylates, and phenates, wherein the amount of metalpresent exceeds the stoichiometric amount. Such salts may have aconversion level in excess of 100% (i.e., they may comprise more than100% of the theoretical amount of metal needed to convert the acid toits “normal,” “neutral” salt). The expression “metal ratio,” oftenabbreviated as MR, is used to designate the ratio of total chemicalequivalents of metal in the overbased salt to chemical equivalents ofthe metal in a neutral salt according to known chemical reactivity andstoichiometry. In a normal or neutral salt, the metal ratio is one andin an overbased salt, the MR, is greater than one. Such salts arecommonly referred to as overbased, hyperbased, or superbased salts andmay be salts of organic sulfur acids, carboxylic acids, or phenols.

The overbased detergent may have a metal ratio of from 1.1:1, or from2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

In some embodiments, a detergent can be used for reducing or preventingrust in a gear, axle, or engine.

In preferred embodiments, one or more detergents can be used to extendthe functional life of elastomeric seals when included in the lubricantcompositions of the present invention. Suitable detergents for extendingthe functional life of elastomeric seals include those detergents thatcomprise a sulfonate or a phenate. Examples of such detergents includeoverbased or neutral calcium or magnesium sulfonate detergents andoverbased or neutral calcium or magnesium phenate detergents.

The detergent may be present at about 0 wt. % to about 10 wt. %, orabout 0.1 wt. % to about 8 wt. %, or about 1 wt. % to about 4 wt. %, orgreater than about 4 wt. % to about 8 wt. % based on the total weight ofthe lubricant composition.

Dispersants

The lubricant composition may optionally further comprise one or moredispersants or mixtures thereof. Dispersants are often known asashless-type dispersants because, prior to mixing in a lubricating oilcomposition, they do not contain ash-forming metals and they do notnormally contribute any ash when added to a lubricant. Ashless-typedispersants are characterized by a polar group attached to a relativelyhigh molecular or weight hydrocarbon chain. Typical ashless dispersantsinclude N-substituted long chain alkenyl succinimides. Examples ofN-substituted long chain alkenyl succinimides include polyisobutylenesuccinimide with number average molecular weight of the polyisobutylenesubstituent in a range of about 350 to about 5000, or about 500 to about3000. Succinimide dispersants and their preparation are disclosed, forinstance in U.S. Pat. Nos. 7,897,696 and 4,234,435. Succinimidedispersants are typically an imide formed from a polyamine, typically apoly(ethyleneamine).

In some embodiments the lubricant composition comprises at least onepolyisobutylene succinimide dispersant derived from polyisobutylene withnumber average molecular weight in the range about 350 to about 5000, orabout 500 to about 3000. The polyisobutylene succinimide may be usedalone or in combination with other dispersants.

In some embodiments, polyisobutylene (PIB), when included, may havegreater than 50 mol %, greater than 60 mol %, greater than 70 mol %,greater than 80 mol %, or greater than 90 mol % content of terminaldouble bonds. Such a PIB is also referred to as highly reactive PIB(“HR-PIB”). HR-PIB having a number average molecular weight ranging fromabout 800 to about 5000 is suitable for use in embodiments of thepresent disclosure. Conventional non-highly reactive PIB typically hasless than 50 mol %, less than 40 mol %, less than 30 mol %, less than 20mol %, or less than 10 mol % content of terminal double bonds.

An HR-PIB having a number average molecular weight ranging from about900 to about 3000 may be suitable. Such an HR-PIB is commerciallyavailable, or can be synthesized by the polymerization of isobutene inthe presence of a non-chlorinated catalyst such as boron trifluoride, asdescribed in U.S. Pat. Nos. 4,152,499 and 5,739,355. When used in theaforementioned thermal ene reaction, HR-PIB may lead to higherconversion rates in the reaction, as well as lower amounts of sedimentformation, due to increased reactivity.

One class of suitable dispersants may be Mannich bases. Mannich basesare materials that are formed by the condensation of a higher molecularweight, alkyl substituted phenol, a polyalkylene polyamine, and analdehyde such as formaldehyde. Mannich bases are described in moredetail in U.S. Pat. No. 3,634,515.

A suitable class of dispersants may be high molecular weight esters orhalf ester amides.

The dispersants may also be post-treated by conventional methods byreaction with any of a variety of agents. Among these agents are boron,urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes,ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides,maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates,hindered phenolic esters, and phosphorus compounds. U.S. Pat. Nos.7,645,726; 7,214,649; and 8,048,831 describe some suitablepost-treatment methods and post-treated products.

The dispersant, if present, can be used in an amount sufficient toprovide up to about 20 wt. %, based upon the total weight of thelubricating oil composition. The amount of the dispersant that can beused may be about 0.1 wt. % to about 15 wt. %, or about 0.1 wt. % toabout 10 wt. %, or about 3 wt. % to about 10 wt. %, or about 1 wt. % toabout 6 wt. %, or about 7 wt. % to about 12 wt. %, based upon the totalweight of the lubricating oil composition. In an embodiment, thelubricating oil composition utilizes a mixed dispersant system.

Extreme Pressure Agents

The lubricating oil compositions herein also may optionally contain oneor more extreme pressure agents. Extreme Pressure (EP) agents that aresoluble in the oil include sulfur- and chlorosulfur-containing EPagents, chlorinated hydrocarbon EP agents and phosphorus EP agents.Examples of such EP agents include chlorinated waxes; organic sulfidesand polysulfides such as dibenzyldisulfide, bis(chlorobenzyl) disulfide,dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurizedalkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurizedDiels-Alder adducts; phosphosulfurized hydrocarbons such as the reactionproduct of phosphorus sulfide with turpentine or methyl oleate;phosphorus esters such as the dihydrocarbyl and trihydrocarbylphosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexylphosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecylphosphite, distearyl phosphite and polypropylene substituted phenylphosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate andbarium heptylphenol diacid; amine salts of alkyl and dialkylphosphoricacids, including, for example, the amine salt of the reaction product ofa dialkyldithiophosphoric acid with propylene oxide; and mixturesthereof.

In one embodiment, the organic polysulfides are S-3 enriched organicpolysulfides. As used herein, the phrase “S-3 enriched organicpolysulfides” refers to organic polysulfides that contain moretrisulfide species than mono-sulfide or other polysulfide species. Insome embodiments, the S-3 enriched organic polysulfides contain at least50 wt % trisulfides, or at least 55%, at least 60%, at least 65%, atleast 75% or at least 80% trisulfides, with the remaining organicpolysulfides being primarily S-2 and S-4 polysulfides. In certainembodiments, the S-3 enriched organic polysulfides contain almost 100%trisulfides. In some embodiments, the molar ratios of S-2:S-3:S-4polysulfides are from about 10-30:50-80:10-30. In certain embodiments,the S-3 enriched organic polysulfides have hydrocarbyl groups eachindependently having from about 2 to about 30 carbons or from about 2 toabout 20 carbons, or from about 2 to about 12 carbons or from about 3 toabout 6 carbons. The hydrocarbyl groups can be aromatic or aliphatic,but are preferably aliphatic. In certain embodiments, the hydrocarbylgroups are alkyl groups. In one embodiment, the S-3 enriched organicpolysulfides comprise at least 60% dihydrocarbyl trisulfide. In otherembodiments, the organic polysulfides by weight % of the totalpolysulfides are from about 5 wt % to about 20 weight % S-2; from about30 wt % to about 80 wt % S-3, and from about 5 wt % to about 50 wt %S-4. Examples of suitable S-3 enriched organic polysulfides includethose disclosed in U.S. Pat. Nos. 6,642,187, 6,689,723, or U.S. Pat. No.6,489,271.

Friction Modifiers

The lubricating oil compositions herein may also optionally contain oneor more additional friction modifiers. Suitable friction modifiers maycomprise metal containing and metal-free friction modifiers and mayinclude, but are not limited to, imidazolines, amides, amines,succinimides, alkoxylated amines, alkoxylated ether amines, amineoxides, amidoamines, nitriles, betaines, quaternary amines, imines,amine salts, amino guanidines, alkanolamides, phosphonates,metal-containing compounds, glycerol esters, sulfurized fatty compoundsand olefins, sunflower oil and other naturally occurring plant or animaloils, dicarboxylic acid esters, esters or partial esters of a polyol andone or more aliphatic or aromatic carboxylic acids, and the like.

Suitable friction modifiers may contain hydrocarbyl groups that areselected from straight chain, branched chain, or aromatic hydrocarbylgroups or mixtures thereof, and may be saturated or unsaturated. Thehydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range fromabout 12 to about 25 carbon atoms. In a embodiments the frictionmodifier may be a long chain fatty acid ester. In an embodiment the longchain fatty acid ester may be a mono-ester, or a di-ester, or a(tri)glyceride. The friction modifier may be a long chain fatty amide, along chain fatty ester, a long chain fatty epoxide derivative, or a longchain imidazoline.

Other suitable friction modifiers may include organic, ashless(metal-free), nitrogen-free organic friction modifiers. Such frictionmodifiers may include esters formed by reacting carboxylic acids andanhydrides with alkanols and generally include a polar terminal group(e.g. carboxyl or hydroxyl) covalently bonded to an oleophilichydrocarbon chain. An example of an organic ashless nitrogen-freefriction modifier is known generally as glycerol monooleate (GMO) whichmay contain mono-, di-, and tri-esters of oleic acid. Other suitablefriction modifiers are described in U.S. Pat. No. 6,723,685.

Aminic friction modifiers may include amines or polyamines. Suchcompounds can have hydrocarbyl groups that are linear, either saturatedor unsaturated, or a mixture thereof and may contain from about 12 toabout 25 carbon atoms. Further examples of suitable friction modifiersinclude alkoxylated amines and alkoxylated ether amines. Such compoundsmay have hydrocarbyl groups that are linear, either saturated,unsaturated, or a mixture thereof. They may contain from about 12 toabout 25 carbon atoms. Examples include ethoxylated amines andethoxylated ether amines.

The amines and amides may be used as such or in the form of an adduct orreaction product with a boron compound such as a boric oxide, boronhalide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.Other suitable friction modifiers are described in U.S. Pat. No.6,300,291.

A friction modifier may be present in amounts of about 0 wt. % to about10 wt. %, or about 0.01 wt. % to about 8 wt. %, or about 0.1 wt. % toabout 4 wt. %, based on the total weight of the lubricant composition.

Viscosity Index Improvers

The lubricating oil compositions herein also may optionally contain oneor more viscosity index improvers. Suitable viscosity index improversmay include polyolefins, olefin copolymers, ethylene/propylenecopolymers, polyisobutenes, hydrogenated styrene-isoprene polymers,styrene/maleic ester copolymers, hydrogenated styrene/butadienecopolymers, hydrogenated isoprene polymers, alpha-olefin maleicanhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, ormixtures thereof. Viscosity index improvers may include star polymersand suitable examples are described in US Publication No. 2012/0101017A1.

The lubricating oil compositions herein also may optionally contain oneor more dispersant viscosity index improvers in addition to a viscosityindex improver or in lieu of a viscosity index improver. Suitabledispersant viscosity index improvers may include functionalizedpolyolefins, for example, ethylene-propylene copolymers that have beenfunctionalized with the reaction product of an acylating agent (such asmaleic anhydride) and an amine; polymethacrylates functionalized with anamine, or esterified maleic anhydride-styrene copolymers reacted with anamine.

The total amount of viscosity index improver and/or dispersant viscosityindex improver may be about 0 wt. % to about 20 wt. %, about 0.1 wt. %to about 15 wt. %, about 0.1 wt. % to about 12 wt. %, or about 0.5 wt. %to about 10 wt. % based on the total weight, of the lubricatingcomposition.

Effective amounts of the various additive components for a specificformulation may be readily ascertained, but for illustrative purposesthese general guides for representative effective amounts are provided.The amounts below are given in weight % of the finished fluid.

Example Ranges Example Ranges Component (wt %) (wt %) A compound offormula (I) 0-10 0.3-5 Dispersant 0-20 0.5-8 Extreme Pressure Agent 0-52-4 Rust Inhibitor 0-1.0 0.05-1.0 Corrosion Inhibitor 0-5 0.05-3Demulsifier 0-5 0.005-1.0 Antifoam Agent 0-0.5 0.001-0.1 Diluent 0-101.0-5.0 Lubricating Base Oil Balance Balance

The compounds of the present invention, and lubricant additivecompositions comprising the same, can be used in automotive gear or axleoils. Typical of such oils are automotive spiral-bevel and worm-gearaxle oils which operate under extreme pressures, load and temperatureconditions, hypoid gear oils operating under both high speed, low-torqueand low-speed, high torque conditions.

Industrial lubrication applications in which the compounds of thepresent invention, and lubricant additive compositions comprising thesame, can be used include hydraulic oils, industrial gear oils, slidewaymachines oils, circulation oils and steam turbine oils, gas turbineoils, for heavy-duty gas turbines and aircraft gas turbines, waylubricants, gear oils, compressor oils, mist oils and machine toollubricants. Engine oils are also contemplated such as passenger carmotor oils, heavy duty diesel engine oils, marine engine oils,locomotives, and high speed automotive diesel engines.

Functional fluids can also be prepared from the compounds of the presentinvention and lubricant additive compositions comprising the same. Thesefluids include automotive fluids such as manual transmission fluids,automatic transmission fluids, continuously variable transmissionfluids, power steering fluids and power brake fluids.

Compounds of the present invention can also be incorporated into greasessuch as automotive, industrial and aviation greases, and automobilechassis lubricants.

The invention also provides a method of lubricating metal surfaces.Lubricating metal surfaces with lubricant compositions of the presentinvention can reduce wear between the metal surfaces when moving. In oneembodiment, the metal surfaces being lubricated can be a machine part.The machine part can comprise an axle, a differential, an engine, amanual transmission, an automatic transmission, a continuously variabletransmission, a crankshaft, a clutch, a hydraulic apparatus, anindustrial gear, a slideway apparatus, and a turbine.

The invention further provides for a method of lubricating a driveline,industrial, or metalworking device comprising lubricating the driveline,industrial or metalworking device with a lubricant compositioncomprising a compound of the present invention.

Seals

Seals are used in the design and manufacture of a multitude of machinesincluding engines, gear assemblies and transmissions to maintain thefluid or lubricant within the apparatus. Machine failures are not causedonly by surface fatigue but also because of lubrication issues. Thus,seals play a critical role in decreasing loss of lubrication, reducingcontaminant ingress, and increasing equipment runtime. The seals come incontact with the lubricant and can, under certain operating conditions,lose their elasticity and become brittle. Often the rate ofdeterioration of the seals is affected by the additives present in thelubricant. Seals are typically made of polymeric materials includingnitrile rubber, silicone, ethylene acrylate, fluoroelastomers andpolyacrylates. Extending the functional life of elastomeric seals candecrease machine wear and downtime, thus increasing productivity andmachine lifetime. The present invention provides methods for extendingthe functional life of elastomeric seals that contact a lubricating orfunctional fluid composition, the method comprising contacting the sealwith an effective amount of a lubricating composition of the presentinvention. Standard testing of seals is well known in the art for bothstatic and dynamic wear and durability. Standard testing methodologiesare readily ascertainable by the skilled artisan.

Although certain embodiments of the present invention may be describedindividually herein, it is understood by the skilled artisan that anyone embodiment can be combined with any other embodiment or embodiments,and such combinations are within the scope of the instant invention.

Synthetic Schemes

The compounds of the present invention can be prepared using syntheticmethods generally known to those skilled in the art and moreparticularly using general synthetic schemes such as those described inU.S. application Ser. No. 14/830,719 filed Aug. 19, 2015 and U.S.application Ser. No. 15/163,481 filed May 24, 2016, each of which arehereby incorporated by reference in their entireties.

Certain compounds of the present invention can be prepared using thefollowing generic schemes:

In certain instances, the synthesis of compounds can result in theproduction of positional isomers. For example, both primary andsecondary alcohols can be formed by a single reaction as follows:

Compounds prepared by the methods illustrated in the above schemes canbe prepared to enrich certain reaction products. However, in certainembodiments, the reaction products are a mixture of products. Forexample, the reaction product of the methods described in scheme 2 maybe a mixture of the P2a and the P3a product. Similarly, the reactionproduct from scheme 4 can be a mixture of one or more of the P5a, P6aand P7a product. Likewise, some amount of the reactants may be presentin the reaction product. The skilled artisan can readily ascertain thecompounds produced from these methods and the mixtures that can result.In the event that a single reaction product is desired, the skilledartisan can employ routine and conventional methods for purifying suchreaction products. Purified products and mixtures that result frommethods such as those described above are within the scope of thepresent invention.

The structures shown in the Intermediates and Examples below are thestructures of the most abundant isomers produced in the particularreactions described. The skilled artisan appreciates and understandsthat the above epoxide addition reaction and reactions similar theretoproduce compounds as secondary alcohols (P1a). However, the same epoxideaddition reaction can form some amount of primary alcohols (P1b).Therefore, the resulting product of the epoxide addition reactions canbe a mixture of positional isomers. For the sake of simplicity, only thesecondary alcohols and the reaction products therefrom are shown belowin Intermediates and Examples. However, all positional isomers of theIntermediates and Examples are within the scope of the invention as aresult of these types of reactions.

INTERMEDIATES AND EXAMPLES

The presence of all Intermediates and Examples can be confirmed by 31PNMR, and was confirmed where indicated.

Intermediates

Synthesis of Intermediate P1-A: O,O-bis(4-methylpentan-2-yl) S-hydrogenphosphorothioate (0.25 mol) is heated to 40° C. and propylene oxide(0.25 mol) is added slowly so as to keep the reaction temperature below50° C. The reaction mixture is then cooked at 50° C. for 30 minutes.Intermediate P1-A is the reaction product.

Synthesis of Intermediate P1-B: P1-B can be made in a process similar toP1-A except O,O-bis(4-methylpentan-2-yl) S-hydrogen phosphorothioate isreplaced with O,O-bis(isopropyl) S-hydrogen phosphorothioate.Intermediate P1-B is the reaction product.

Synthesis of Intermediate P1-C: P1-C can be made in a process similar toP1-A except O,O-bis(4-methylpentan-2-yl) S-hydrogen phosphorothioate isreplaced with O,O-bis(2-ethylhexyl) S-hydrogen phosphorothioate.Intermediate P1-C is the reaction product.

Synthesis of Intermediate P1-D: P1-D can be made in a process similar toP1-A except O,O-bis(4-methylpentan-2-yl) S-hydrogen phosphorodthioate isreplaced with O,O-bis(isobutyl) S-hydrogen phosphorothioate.Intermediate P1-D is the reaction product.

Synthesis of Intermediate P3-A: P1-A (1.68 moles) is combined withO,O-di-isopropyl S-hydrogen phosphorothioate (0.84 moles; used assupplied by Cheminova) in a round bottomed flask equipped with amagnetic stirring bar. The reaction contents is heated to 90° C. underreduced pressure (10 mm Hg).

Throughout the reaction isopropanol is distilled off and collected intoa separate cooled vessel. After 6.5 hours the reaction contents werecooled to 10° C. and propylene oxide (0.84 moles; Sigma Aldrich) slowlyadded to the stirring reaction over a 45 minute period. P3-A is thereaction product.

Synthesis of Intermediates P3-B, P3-C and P3-D: P3-B, P3-C and P3-D canbe prepared similarly to P3-A, with the exception that P1-A is replacedwith P1-B, P1-C and P1-D, respectively.

Synthesis of Intermediate P4-A: Intermediate P3-A is prepared as above.To the reaction, O,O-di-isopropyl S-hydrogen phosphorothioate (376 g,1.76 moles; used as supplied by Cheminova) is added and the reactionmixture heated at 90° C. and 10 mm Hg of pressure for 6 hours beforecooling to room temperature. P4-A is the reaction product.

Synthesis of Intermediates P4-B, P4-C and P4-D: P4-B, P4-C and P4-D canbe made similarly to P4-A, with the exception that P3-A is replaced withP3-B, P3-C and P3-D, respectively.

Synthesis of intermediate P7-A: P3-A (0.4 moles) is combined withO,O-di-isopropyl S-hydrogen phosphorothioate (0.2 moles; used assupplied by Cheminova) and the reaction mixture is heated at 90° C. and10 mm Hg of pressure for 6 hours before cooling to room temperature.P7-A is the reaction product.

Synthesis of intermediates P7-B, P7-C and P7-D: P7-B, P7-C and P7-D canbe prepared similarly to P7-A, with the exception that P3-A is replacedwith P3-B, P3-C and P3-D, respectively.

EXAMPLES Example 1

Intermediate P1-A (1.68 moles) is combined with O,O-di-isopropylS-hydrogen phosphorothioate (0.84 moles; used as supplied by Cheminova)in a round bottomed flask equipped with a magnetic stirring bar. Thereaction contents are heated to 90° C. under reduced pressure (10 mmHg). Throughout the reaction isopropanol is distilled off and collectedinto a separate cooled vessel. After 6.5 hours the reaction contents arecooled to 10° C. and propylene oxide (0.84 moles; Sigma Aldrich) slowlyadded to the stirring reaction over a 45 minute period. At this timeO,O-di-isopropyl S-hydrogen phosphorothioate (1.76 moles; used assupplied by Cheminova) is added and the reaction mixture heated at 90°C. and 10 mm Hg of pressure for 6 hours before cooling to roomtemperature. Ethyl acrylate (2.7 moles; Dow Chemical) is next added tothe reaction and the temperature brought to 70° C. for 2 hours.Subsequently, the reaction is brought to 80° C. and a 100 mm Hg vacuumapplied until ethyl acrylate no longer distills off into the cold trap.

Example 2

Intermediate P3-A (0.4 moles) is combined with O,O-di-isopropylS-hydrogen phosphorothioate (0.2 moles; used as supplied by Cheminova)and the reaction mixture heated at 90° C. and 10 mm Hg of pressure for 6hours before cooling to room temperature. Ethyl acrylate (0.2 moles; DowChemical) is next added to the reaction and the temperature brought to70° C. for 2 hours. Subsequently, the reaction is brought to 80° C. anda 100 mm Hg vacuum applied until ethyl acrylate no longer distills offinto the cold trap.

Example 3

Intermediate P4-A (0.2 moles) is combined with acrylic acid (0.19 moles)and the reaction left to stir at 70° C. for two hours before applying a10 mm Hg vacuum to strip off any remaining volatiles.

Example 4

Intermediate P7-A (0.11 moles) is combined with acrylic acid (0.1 moles)and the reaction left to stir at 70° C. for two hours before applying a10 mm Hg vacuum to strip off any remaining volatiles.

Example 5

The compound of Example 5 is prepared as in Example 3 except P4-A isreplaced with P4-B.

Example 6

The compound of Example 6 is prepared as in Example 4 except P7-A isreplaced with P7-B.

Example 7

The compound of Example 7 is prepared as in Example 1 except P1-A isreplaced with P1-B.

Example 8

The compound of Example 8 is prepared as in Example 2 except P3-A isreplaced with P3-B.

Example 9

The compound of Example 9 is prepared as in Example 3 except P4-A isreplaced with P4-C

Example 10

The compound of Example 10 is prepared as in Example 4 except P7-A isreplaced with P7-C.

Example 11

The compound of Example 11 is prepared as in Example 1 except P1-A isreplaced with P1-C.

Example 12

The compound of Example 12 is prepared as in Example 2 except P3-A isreplaced with P3-C.

Example 13

The compound of Example 13 is prepared as in Example 3 except P4-A isreplaced with P4-D

Example 14

The compound of Example 14 is prepared as in Example 4 except P7-A isreplaced with P7-D.

Example 15

The compound of Example 15 is prepared as in Example 1 except P1-A isreplaced with P1-D.

Example 16

The compound of Example 16 is prepared as in Example 2 except P3-A isreplaced with P3-D.

Example 17

Example 17 is prepared as in Example 1 except the ethyl acrylate isreplaced with methyl acrylate.

Example 18

Example 18 is prepared as in Example 2 except the ethyl acrylate isreplaced with methyl acrylate.

Example 19

Example 19 is prepared as in Example 7 except the ethyl acrylate isreplaced with methyl acrylate.

Example 20

Example 20 is prepared as in Example 8 except the ethyl acrylate isreplaced with methyl acrylate.

Example 21

Example 21 is prepared as in Example 11 except the ethyl acrylate isreplaced with methyl acrylate.

Example 22

Example 22 is prepared as in Example 12 except the ethyl acrylate isreplaced with methyl acrylate.

Example 23

Example 23 is prepared as in Example 15 except the ethyl acrylate isreplaced with methyl acrylate.

Example 24

Example 24 is prepared as in Example 16 except the ethyl acrylate isreplaced with methyl acrylate.

Example 25. Amine Carboxylate Salt

The compound of Example 3 can be treated with an amine containingcompound, for example octylamine or oleylamine, at such a treat ratethat TAN=TBN to produce an amine carboxylate salt. The compound ofExample 3 can be added to a suitable reaction vessel under stirring. Tothis the amine containing compound can be added slowly so as to controlthe exothermic event.

Example 26

Intermediate P1-A is prepared as above exceptO,O-bis(4-methylpentan-2-yl) S-hydrogen phosphorothioate is replacedwith bis(4-methylpentan-2-yl) hydrogen phosphate. The reaction product(1.68 moles) is combined with O,O-di-isopropyl S-hydrogenphosphorothioate (0.84 moles; used as supplied by Cheminova) in a roundbottomed flask equipped with a magnetic stirring bar. The reactioncontents are heated to 90° C. under reduced pressure (10 mm Hg).Throughout the reaction isopropanol is distilled off and collected intoa separate cooled vessel. After 6.5 hours the reaction contents arecooled to 10° C. and propylene oxide (0.84 moles; Sigma Aldrich) slowlyadded to the stirring reaction over a 45 minute period. At this timeO,O-di-isopropyl S-hydrogen phosphorothioate (1.76 moles; used assupplied by Cheminova) is added and the reaction mixture heated at 90°C. and 10 mm Hg of pressure for 6 hours before cooling to roomtemperature. Ethyl acrylate (2.7 moles; Dow Chemical) is next added tothe reaction and the temperature brought to 70° C. for 2 hours.Subsequently, the reaction is brought to 80° C. and a 100 mm Hg vacuumapplied until ethyl acrylate no longer distills off into the cold trap.

Example 27

Intermediate P3-A is prepared as above except O,O-di-isopropylS-hydrogen phosphorothioate is replaced with bis(4-methylpentan-2-yl)hydrogen phosphate. The product (0.4 moles) is combined withO,O-di-isopropyl S-hydrogen phosphorothioate (0.2 moles; used assupplied by Cheminova) and the reaction mixture heated at 90° C. and 10mm Hg of pressure for 6 hours before cooling to room temperature. Ethylacrylate (0.2 moles; Dow Chemical) is next added to the reaction and thetemperature brought to 70° C. for 2 hours. Subsequently, the reaction isbrought to 80° C. and a 100 mm Hg vacuum applied until ethyl acrylate nolonger distills off into the cold trap.

Example 28

P3-A is prepared as above except O,O-di-isopropyl S-hydrogenphosphorothioate is replaced with bis(4-methylpentan-2-yl) hydrogenphosphate. To the reaction product, O,O-di-isopropyl S-hydrogenphosphorothioate (1.76 moles; used as supplied by Cheminova) is addedand the reaction mixture heated at 90° C. and 10 mm Hg of pressure for 6hours before cooling to room temperature. The reaction product (0.2moles) is combined with acrylic acid (0.19 moles) and the reaction leftto stir at 70° C. for two hours before applying a 10 mm Hg vacuum tostrip off any remaining volatiles.

Example 29

The compound of Example 29 is prepared as in Example 27, except that theethyl acrylate is replaced with acrylic acid (0.1 moles) and thereaction left to stir at 70° C. for two hours before applying a 10 mm Hgvacuum to strip off any remaining volatiles.

Other embodiments of the present disclosure will be apparent to thoseskilled in the art from consideration of the specification and practiceof the embodiments disclosed and suggested herein. It is intended thatthe specification and examples be considered as exemplary only, with atrue scope and spirit of the disclosure being indicated by the followingclaims.

1-31. (canceled)
 32. A compound of formula (I)

or a tribologically acceptable salt thereof, wherein A is:

each R¹ is the same or different and is independently selected fromalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl, whereinsaid aryl and aralkyl are optionally substituted with one to threesubstituents each independently selected from alkyl and alkenyl; each R²and R³ are independently selected from H, alkyl, alkenyl, cycloalkyl andcycloalkylalkyl; Y is selected from the group consisting of alkyl,alkoxyalkyl, benzyl, and —R⁴-R⁵-R⁶; R⁴ is alkylene; R⁵ is selected fromthe group consisting of a bond, alkylene; —C(O)— and —C(R⁷)—; R⁶ isselected from the group consisting of alkyl, hydroxyalkyl,hydroxyalkyleneoxy, hydroxy and alkoxy; R⁷ is hydroxy; m is an integerfrom 2 to 8; X₁ is R⁸ or Z; X₂ is selected from the group consisting ofR⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl;and Z is

wherein when X₂ is R⁸, X₁ is Z; and wherein W₁-W₁₂ are eachindependently O or S, and at least one of W₁-W₁₂ is O.
 33. The compoundof claim 32, wherein the compound is a compound of formula (Ia)

or a tribologically acceptable salt thereof, each R¹ is the same ordifferent and is independently selected from alkyl, alkenyl, cycloalkyl,cycloalkylalkyl, aryl, and aralkyl, wherein said aryl and aralkyl areoptionally substituted with one to three substituents each independentlyselected from alkyl and alkenyl; each R² is independently selected fromalkyl, alkenyl, cycloalkyl and cycloalkylalkyl; Y is selected from thegroup consisting of alkyl, alkoxyalkyl, benzyl, and —R⁴-R⁵-R⁶; R⁴ isalkylene; R⁵ is selected from the group consisting of a bond, alkylene;—C(O)— and —C(R⁷)—; R⁶ is selected from the group consisting of alkyl,hydroxyalkyl, hydroxyalkyleneoxy, hydroxy and alkoxy; R⁷ is hydroxy; X₂is selected from the group consisting of R⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl; Zis

and W₁-W₁₄ are each independently O or S, and at least one of W₁-W₁₄ isO.
 34. The compound of claim 32, wherein each R¹ is the same ordifferent and is independently selected from C₁-C₃₀alkyl, C₂-C₃₀alkenyl,cycloalkyl, cycloalkylalkyl, aryl and aralkyl, wherein said aryl andaralkyl are optionally substituted with one to three substituents eachindependently selected from C₁-C₁₀alkyl and C₂-C₁₀alkenyl.
 35. Thecompound of claim 32, wherein Y is —R⁴-R⁵-R⁶.
 36. The compound of claim35, wherein R⁵ is —C(O)—.
 37. The compound of claim 32, wherein R² isC₁-C₁₀alkyl.
 38. The compound of claim 32, wherein X₂ is

or R⁸.
 39. The compound of claim 32, wherein the compound is a compoundof formula (II)

or a tribologically acceptable salt thereof, wherein A is:

each R¹ is the same or different and is independently selected fromalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl, whereinsaid aryl and aralkyl are optionally substituted with one to threesubstituents each independently selected from alkyl and alkenyl; each R²and R³ are independently selected from H, alkyl, alkenyl, cycloalkyl andcycloalkylalkyl; Y is selected from the group consisting of alkyl,alkoxyalkyl, benzyl, and —R⁴-R⁵-R⁶; R⁴ is alkylene; R⁵ is selected fromthe group consisting of a bond, alkylene; —C(O)— and —C(R⁷)—; R⁶ isselected from the group consisting of alkyl, hydroxyalkyl,hydroxyalkyleneoxy, hydroxy and alkoxy; R⁷ is hydroxy; m is an integerfrom 2 to 8; X₁ is R⁸ or Z; X₂ is selected from the group consisting ofR⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl;and Z is

wherein when X₂ is R⁸, X₁ is Z; and wherein W₁, W₃, W₅, W₇, W₉, and W₁₁are each independently O or S, and at least one of W₁, W₃, W₅, W₇, W₉,and W₁₁ is O.
 40. The compound of claim 39, wherein the compound offormula (II) is a compound of formula (IIa):

or a tribologically acceptable salt thereof, each R¹ is the same ordifferent and is independently selected from alkyl, alkenyl, cycloalkyl,cycloalkylalkyl, aryl, and aralkyl, wherein said aryl and aralkyl areoptionally substituted with one to three substituents each independentlyselected from alkyl and alkenyl; each R² is independently selected fromalkyl, alkenyl, cycloalkyl and cycloalkylalkyl; Y is selected from thegroup consisting of alkyl, alkoxyalkyl, benzyl, and —R⁴-R⁵-R⁶; R⁴ isalkylene; R⁵ is selected from the group consisting of a bond, alkylene;—C(O)— and —C(R⁷)—; R⁶ is selected from the group consisting of alkyl,hydroxyalkyl, hydroxyalkyleneoxy, hydroxy and alkoxy; R⁷ is hydroxy; X₂is selected from the group consisting of R⁸,

R⁸ is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl,wherein said aryl and aralkyl are optionally substituted with one tothree substituents each independently selected from alkyl and alkenyl;and Z is

W₁, W₃, W₅, W₇, W₉, W₁₁ and W₁₄ are each independently O or S, and atleast one of W₁, W₃, W₅, W₇, W₉, W₁₁ and W₁₄ is O.
 41. The compound ofclaim 39, wherein each R¹ is the same or different and is independentlyselected from C₁-C₃₀alkyl, C₂-C₃₀alkenyl, cycloalkyl, cycloalkylalkyl,aryl and aralkyl, wherein said aryl and aralkyl are optionallysubstituted with one to three substituents each independently selectedfrom C₁-C₁₀alkyl and C₂-C₁₀alkenyl.
 42. The compound of claim 39,wherein R² is C₁-C₁₀alkyl.
 43. The compound of claim 39, wherein X₂ is

or R⁸.
 44. The compound of claim 32, selected from


45. A lubricant additive composition comprising a compound of claim 32.46. A lubricant composition comprising: a) a base oil; and b) a compoundof claim 32, and wherein the base oil is a major amount of thecomposition.
 47. A method of lubricating moving metal surfacescomprising lubricating the metal surfaces with a lubricant compositionof claim
 46. 48. A method of reducing wear between moving metal surfacesof a machine part comprising lubricating the machine part with alubricant composition comprising: a) a major amount of an oil oflubricating viscosity; and b) an effective amount of a compound of claim32.